The Thiele‐Winter Acetoxylation of Quinones

In 1898, Johannes Thiele described the reaction of p-benzoquinone with acetic acid in the presence of a small quantity of sulfuric acid to give 1,2,4-triacetoxybenzene in 80% yield. Later Thiele and Winter described further experiments that showed both 1,2- and 1,4-naphthoquinone gave 1,2,4-triacetoxynaphthalene and that the same product was obtained when sulfuric acid was replaced by zinc chloride. Thiele-Winter acetoxylation can be defined as the acid-catalyzed reactions of quinones with acetic acid to give triacetoxy aromatic compounds. This reaction has been carried out on a large number of quinones and to this point there has been no review. Very little work has been done on the reaction of quinones with anhydrides other than acetic anhydride. Results of these studies are summarized. Reactions with other anhydrides are discussed. Keywords: Thiele-Winter acetoxylation; quinones; benzoquinones; naphthoquinones; anhydride; triacetates; butylquinones; methylquinones; experimental procedures

[1]  Yuan-Qiang Chen.  New Criteria on Exponential Stability of Uncertain Delayed Systems with Multiple Delays and Parameter Uncertainty , 2011 .

[2]  F. Kögl,et al.  Untersuchungen über Pilzfarbstoffe XIV : Über Oosporein, den Farbstoff von Oospora colorans van Beyma† , 2010 .

[3]  J. Overeem,et al.  Mollisin, a naturally occurring chlorine-containing quinone: Part IV,. Revised structures for cochenillic acid and for the insect pigments, carminic and kermesic acids†‡ , 2010 .

[4]  K. Folkers,et al.  New substituted 2,3-dimethoxy-1,4-benzoquinones as inhibitors of coenzyme Q systems. , 1971, Journal of medicinal chemistry.

[5]  Teruo Hayashi,et al.  The structure of miltirone, a new diterpenoid quinone , 1970 .

[6]  W. Steglich,et al.  Pilzpigmente, IV. Anthrachinon‐Pigmente aus Dermocybe sanguinea (Wulf. ex Fr.) Wünsche und D. semisanguinea (Fr.) , 1969 .

[7]  H. Musso,et al.  Zur Autoxydation von Resorcinderivaten. Über die Bildung von Hydroxy-tert.-butyl-chinonen und deren Abbau zu Cyclopentenon-Derivaten durch Alkali , 1969 .

[8]  J. B. Searle,et al.  Thiele acetylation of quinones. Part III. p-Benzoquinones with bromo- and methoxy-substituents , 1969 .

[9]  M. Watts,et al.  Biphenylenes. Part XXII. Reactions of 1,2,7,8-tetramethoxy-4,5-dimethyl- and 2,3,6,7-tetramethoxybiphenylene and of 1,6,7,8-tetramethoxybiphenylene-2,3-quione , 1969 .

[10]  J. B. Searle,et al.  Thiele acetylation of quinones. Part II. p-Benzoquinones with halogen substituents , 1969 .

[11]  P. Scheuer,et al.  Synthesis of juglone derivatives : Hydroxy, acetyl and ethyl substituents , 1969 .

[12]  Hans‐Werner Wanzlick,et al.  Synthesen mit naszierenden Chinonen, IV. Basenkatalysierte Alkoholaddition an in situ erzeugte o-Chinone , 1968 .

[13]  S. Ukai,et al.  Reaction of Phenol Derivatives with Sulfoxides. III. Synthesis and Characterization of 2-Alkylthioand 2-Arylthio-5-hydroxy-p-benzoquinones , 1968 .

[14]  A. Fatiadi.  Acetic anhydride—phosphoric acid as an acetylating agent , 1968 .

[15]  Mauri Lounasmaa,et al.  Sur les Réactions des Quinones avec l'Anhydride Acétique en Présence d'Acétate de Sodium. Partie VI. Sur les Réactions de la 3,5-Di-tert.butyl-o-benzoquinone et de la 5-tert.Butyl-3-méthyl-o-benzoquinone. , 1968 .

[16]  H. S. Wilgus,et al.  Thiele acetylation of substituted benzoquinones , 1967 .

[17]  H. Teuber,et al.  Reaktionen mit Nitrosodisulfonat, XXXVI. Chinolin‐chinone‐(5.6) aus 5‐Hydroxy‐chinolinen , 1967 .

[18]  M. Newman,et al.  Attempted preparation of new phenanthrenequinone types , 1967 .

[19]  R. H. Thomson,et al.  Naturally occurring quinones. Part IX. The chemistry of hydroxyperezone and perezinone , 1967 .

[20]  M. J. Weiss,et al.  The mitomycin antibiotics. Synthetic studies. XII. Indoloquinone analogs with variations at positions 5 and 6. , 1966, Journal of the American Chemical Society.

[21]  J. Corbett.  The chemistry of hydroxyquinones. Part I. The reaction of 2-hydroxybenzoquinones with alkaline hydrogen peroxide , 1966 .

[22]  M. J. Weiss,et al.  The mitomycin antibiotics. Synthetic studies. V. Preparation of 7-methoxymitosene. , 1965, The Journal of organic chemistry.

[23]  C. Hassall,et al.  869. The biosynthesis of phenols. Part IX. Asperugin, a metabolic product of Aspergillus rugulosus , 1965 .

[24]  M. J. Weiss,et al.  The Mitomycin Antibiotics. Synthetic Studies. II.1 The Synthesis of 7-Methoxymitosene, an Antibacterial Agent , 1964 .

[25]  F. Takács.  Über die Einwirkung von Bleitetraacetat auf Phenole, 11. Mitt.: Darstellung neuer o- und p-Benzochinolacetate und o-Chinonondiacetate , 1964 .

[26]  P. Scott,et al.  11. Colouring matters of the Aphididæ. Part XVIII. The structure and chemistry of the erythroaphins , 1964 .

[27]  G. Pettersson,et al.  Synthesis of 2,3-Dihydroxy-5,6-dimethyl-1,4-benzoquinone and its Monomethyl Ether. , 1964 .

[28]  R. Ryhage,et al.  Synthesis of Four Ethyl-dimethylbenzenetriols in Relation to a New Phenolic Metabolite of Penicillium baarnense. , 1964 .

[29]  J. Mcomie,et al.  205. Biphenylenes. Part XI. Some reactions of 1,2,3,6,7,8-hexamethoxybiphenylene , 1964 .

[30]  Philip N. James,et al.  The Mitomycin Antibiotics. Synthetic Studies. I. Synthesis of Model Quinones , 1963 .

[31]  J. Mcomie,et al.  1013. Thiele acetylation of 2-phenyl-1,4-benzoquinone and its 5-methoxy-derivative , 1963 .

[32]  J. Mcomie,et al.  982. Biphenylenes. Part VIII. Synthesis and reactions of 2-hydroxybiphenylene and of biphenylene-2,3-quinone , 1962 .

[33]  H. Schweizer.  Zur Kenntnis der Reaktivität polycyclischer Chinone 3. Mitteilung , 1962 .

[34]  John D. Sanders,et al.  90. Derivatives of stilbenequinone , 1962 .

[35]  H. Hopff,et al.  Zur Kenntnis der Reaktivität polycyclischer Chinone , 1962 .

[36]  L. Horner,et al.  Zur Kenntnis der o-Chinone, XVI. Additionsreaktionen mit 3-Methoxy-o-chinon , 1961 .

[37]  L. Horner,et al.  Zur Kenntnis der o‐Chinone, XVII. Darstellung und Additionsverhalten von o‐Chinonen des 6.7‐Benzotropolons , 1961 .

[38]  H. Budzikiewicz,et al.  Untersuchungen über die Dienon-Phenol-Umlagerung o-chinolider Systeme, 5. Mitt. , 1960 .

[39]  J. Barltrop,et al.  435. The synthesis of tetracyclines. Part I. Some model diene reactions , 1959 .

[40]  J. Pospisil,et al.  Oxydation von brenzcatechin IV. Über die oxydation von 4- tert .-octylbrenzcatechin , 1959 .

[41]  J. C. Sheehan,et al.  The Structure of Terreic Acid , 1958 .

[42]  W. Metlesics.  Reaktionen mit Diacetylsulfid I , 1957 .

[43]  R. Lutz,et al.  A Study of an Oxidative-amination Method for the Synthesis of Aminoquinones1 , 1956 .

[44]  L. Fieser,et al.  Investigation of the Chemical Nature of Gonyleptidine , 1956 .

[45]  B. Thorell,et al.  Synthesis of Compounds Related to Muscarufin. I. , 1956 .

[46]  L. C. Clark,et al.  MESCALINE ANALOGS. II. TETRA- AND PENTA-METHOXY--PHENETHYLAMINES , 1955 .

[47]  A. Robertson,et al.  The chemistry of fungi. Part XXIV. The formation of diquinones , 1955 .

[48]  A. R. Todd,et al.  Colouring matters of the aphididœ. Part IX. Some reactions of extended quinones , 1954 .

[49]  A. Calderbank,et al.  Colouring matters of the aphididœ. Part X. Preparation and properties of 4 : 9-dihydroxyperylene-3 : 10-quinone , 1954 .

[50]  J. Lyons,et al.  582. Quinones. Part III. Addition reactions of 1: 4-naphthaquinones substituted in the 6-position , 1953 .

[51]  John C. Roberts,et al.  654. Studies in mycological chemistry. Part I. Flaviolin, 2(or 3): 5: 7-trihydroxy-1: 4-naphthaquinone, a metabolic product of Aspergillus citricus(Wehmer) Mosseray , 1953 .

[52]  A. Soloway,et al.  Reactions of Peracids. VII. Nuclear Oxidation of Aromatic Ethers with Perbenzoic Acid , 1952 .

[53]  T. Ulbricht,et al.  336. Some reactions of indan-4-ol , 1952 .

[54]  B. Lindberg,et al.  Studies on Quinones and Hydroquinones. II. Monohalogen Derivatives of 2,5- and 2,6-Dimethoxyhydroquinone. , 1952 .

[55]  P. Praill,et al.  137. Acylation reactions catalysed by strong acids. Part VI. A comparison of zinc chloride and perchloric acid as catalysts for the thiele acetylation of quinones , 1952 .

[56]  P. Praill,et al.  482. Addition reactions of quinones. Part II. The so-called uncatalysed addition of acetyl chloride to benzoquinone and tolu-2 : 5-quinone , 1952 .

[57]  R. H. Thomson.  Studies in the Juglone Series. III. Addition Reactions , 1951 .

[58]  W. Mclamore.  Synthesis of Some Hydroxy Alkylbenzoquinones , 1951 .

[59]  C. F. Allen,et al.  ADDITION OF HYDROGEN CHLORIDE TO p-BENZOQUINONES. FAILURE OF ACETYL CHLORIDE TO REACT WITH p-BENZOQUINONE , 1950 .

[60]  B. Lindberg,et al.  On the Reactivity of 2,5- and 2,6-Dimethoxyquinone. , 1950 .

[61]  D. Cram.  Preparation and Reactions of 2-Acyl-3-hydroxy-1,4-naphthoquinones , 1949 .

[62]  L. Fieser,et al.  Naphthoquinone Antimalarials. XXIII. Bz-Substituted Derivatives , 1949 .

[63]  Thomson Rh.  Studies in the juglone series; hydroxy and hydroxyhalogeno derivatives. , 1948 .

[64]  L. Fieser.  Naphthoquinone Antimalarials. III. Diene Synthesis of 1,4-Naphthoquinones1 , 1948 .

[65]  R. H. Thomson.  Studies in the juglone series; some halogen derivatives and their reaction with analine. , 1948, The Journal of organic chemistry.

[66]  E. Winter,et al.  Kinetic studies in the solvents acetic acid and acetic anhydride. Part I.—Properties of the solvo-system , 1948 .

[67]  T. Posternak,et al.  Recherches sur la biochimie des champignons inférieurs V. Nouvelles synthèses de la phoenicine et de l'isophoenicine , 1943 .

[68]  J. C. Mcgowan,et al.  130. Condensation products of phenols and ketones. Part VI. The conversion of an o-quinone into a derivative of pyrogallol , 1943 .

[69]  A. H. Cook,et al.  136. Some alkyl quinols and related compounds , 1942 .

[70]  L. Fieser,et al.  Hydro, oxido and other derivatives of vitamin K1 and related compounds. , 1940 .

[71]  C. Kuroda,et al.  The Pigments from the Sea Urchins and the Syntheses of the Related Compounds , 1940 .

[72]  L. Fieser,et al.  Synthesis of Quinones Related to Vitamins K1 and K2 , 1939 .

[73]  L. Fieser,et al.  4-Alkyl Derivatives of 1,2-Naphthoquinone , 1939 .

[74]  W. K. Anslow,et al.  309. The action of alcoholic monomethylamine on derivatives of benzoquinone and toluquinone. Part I. The methoxy- and hydroxy-methoxy-derivatives , 1939 .

[75]  W. K. Anslow,et al.  Studies in the biochemistry of micro-organisms: Synthesis of spinulosin (3:6-dihydroxy-4-methoxy-2:5-toluquinone) a metabolic product of Penicillium spinulosum Thom. , 1938, The Biochemical journal.

[76]  W. K. Anslow,et al.  Studies in the biochemistry of micro-organisms: Fumigatin (3-hydroxy-4-methoxy-2:5-toluquinone), and spinulosin (3:6-dihydroxy-4-methoxy-2:5-toluquinone), metabolic products respectively of Aspergillus fumigatus Fresenius and Penicillium spinulosum Thom. , 1938 .

[77]  W. K. Anslow,et al.  86. The isomeric dimethoxy-2 : 5-toluquinones and certain related compounds , 1938 .

[78]  T. Posternak.  Recherches sur la biochimie des champignons inférieurs II. sur la constitution et la synthèse de la phoenicine et sur quelques nouveaux dérivés de la 4,4′‐ditoluquinone , 1938 .

[79]  L. Fieser,et al.  The Addition of Dienes to Halogenated and Hydroxylated Naphthoquinones , 1937 .

[80]  L. Fieser,et al.  Application of the Diene Synthesis to Halogenated 1,2- and 3,4-Phenanthrenequinones , 1937 .

[81]  H. Waldmann.  Über 5,6,7,8‐Tetrachlorchinizarin. mit einem Anhang über 5,6,7,8‐Tetrachlor‐1,2‐benzanthrachinon , 1937 .

[82]  L. Fieser,et al.  Concerning the Mechanism of the Hooker Oxidation , 1936 .

[83]  L. Fieser,et al.  Synthesis of Plumbagin , 1936 .

[84]  L. Fieser,et al.  A Comparison of Heterocyclic Systems with Benzene.1IV. Thionaphthenequinones , 1935 .

[85]  L. Fieser,et al.  A Study of the Addition Reactions of Certain Alkylated Naphthoquinones1 , 1934 .

[86]  H. Erdtman.  Studies on the formation of complex oxidation and condensation products of phenols : a contribution to the investigation of the origin and nature of humic acid , 1933 .

[87]  H. Erdtman.  Studies on the formation of complex oxidation and condensation products of phenols. Part II.—Coupling of simple phenols and quinones to diphenyl derivatives , 1933 .

[88]  M. Bogert,et al.  THE CHEMISTRY OF THE ACYL PARA-QUINONES. A CONTRIBUTION TO THE SOLUTION OF THE “PECHMANN DYES” PROBLEM1 , 1930 .

[89]  L. Fieser.  1,2-PHENANTHRENEQUINONE , 1929 .

[90]  L. Fieser.  SOME DERIVATIVES OF 3,4-PHENANTHRENEQUINONE , 1929 .

[91]  A. Green.  CLXXXVI.—The action of thionyl chloride on hydroxyanthraquinones. Part II. Quinizarin , 1926 .

[92]  F. Kehrmann,et al.  Über Oxime von Amino‐ und Oxy‐chinonen der Benzolreihe , 1926 .

[93]  R. Bütler,et al.  Untersuchungen über Derivate des β-Methylanthrachinons. IV. Mitteilung. Über Nitroderivate des β-Methylanthrachinons und einige Umwandlungsprodukte derselben , 1924 .

[94]  G. Rohde,et al.  Über die Konstitution des β‐Bromcarmins , 1910 .

[95]  Richard Willstätter,et al.  Über amphi‐Naphthochinone. II , 1907 .

[96]  J. Thiele.  Ueber die Einwirkung von Essigsäure-anhydrid auf Chinon und auf Dibenzoylstyrol , 1898 .

[97]  O. Hinsberg.  Ueber einige Diphenylsulfonderivate , 1894 .

[98]  H. Schulz.  Ueber die Einwirkung von Säurechloriden und Bromiden auf Chinone , 1882 .